EP0402771A1 - Procédé de dédoublement enzymatique d'esters vinyliques d'acides 2-aryl propioniques - Google Patents
Procédé de dédoublement enzymatique d'esters vinyliques d'acides 2-aryl propioniques Download PDFInfo
- Publication number
- EP0402771A1 EP0402771A1 EP90110794A EP90110794A EP0402771A1 EP 0402771 A1 EP0402771 A1 EP 0402771A1 EP 90110794 A EP90110794 A EP 90110794A EP 90110794 A EP90110794 A EP 90110794A EP 0402771 A1 EP0402771 A1 EP 0402771A1
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- EP
- European Patent Office
- Prior art keywords
- carbonyl
- reaction
- hydrogen
- carbon atoms
- alkyl chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P41/00—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture
- C12P41/003—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by ester formation, lactone formation or the inverse reactions
- C12P41/005—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by ester formation, lactone formation or the inverse reactions by esterification of carboxylic acid groups in the enantiomers or the inverse reaction
Definitions
- EP 153 474 describes the resolution of 2- (6-methoxy-2-naphthyl) propionic acid lower alkyl ester.
- the R-acid is produced by incubating the racemate with lipases from Aspergillus and Bacillus, and in the second stage the remaining S-ester is hydrolyzed with non-specific lipases from pork liver or Pleurotus ostreatus.
- High sales can only be achieved by continuously separating the alcohol released during the cleavage, which would otherwise have an inhibiting effect on the enzyme.
- European patent application 195 717 relates to the production of S-2-arylpropionic acid by incubating the racemic ester with a microbial esterase, in particular Candida cylindracea.
- the ester groups are -CH 2 -C ⁇ CH.
- -CH 2 -CH CH 2 -CH 2 -CN, -CH 2 -COCH 3 , -CH 2 -COO- (C 1 -C 4 ) or -CH 2 -O- (C 1 -C 4 ).
- the sales speed is relatively slow. Approx. 30 hours or more were required for a 40% conversion.
- EP 233 656 also describes the hydrolysis of ⁇ -arylpropionic acid esters in the S configuration with the aid of new bacterial enzymes which have the 10-fold activity of Candida cylindracea.
- the invention thus relates to a process for the enzymatic hydrolysis of 2-arylpropionic acid ester, which is characterized in that the compound of the general formula I in which R 'is a substituted or unsubstituted aryl radical, is incubated with hydrolases.
- the compound of the formula I is particularly preferred in the process according to the invention used in the R 'represents the compound of the formula II or III in which R 2 is hydrogen, a branched or unbranched alkyl chain having 1 to 8 C atoms, alkoxy or benzoyl, where R 3 and R 4 have the meaning given above.
- racemic 2-arylpropionic acids are prepared by known processes (J.P. Rieu et al. See above).
- the vinyl esters of these racemic 2-arylpropionic acids are prepared in a conventional manner, for example by esterification with vinyl acetate in the presence of palladium or mercury catalysts. (R. Wilsontel, Synthesis, 242 (1970)).
- the vinyl esters of racemic 2- (6-methoxy-2-naphthyl) propionic acid (Naproxen @) and 2- (4-isobutylphenyl) propionic acid (Ibuprofeno) are particularly preferably used.
- Lipases, esterases or proteases which are in particular of microbial origin, can be used as hydrolases.
- Lipases or esterases from Pseudomonas, Mucor, Rhizopus, Penicillium, Geotrichum and in particular from Aspergillus, Candida and Bacillus, but also lipases and esterases from pig liver or pig pancreas are preferably used.
- Proteases from Bacillus, Aspergillus and Rhizopus, in particular from Aspergillus oryzae are also preferred.
- the enzymes are largely commercially available or can be obtained from the corresponding sources using conventional methods.
- the microbial enzymes can be isolated, for example, after culturing the microorganisms on conventional nutrient media using known methods. However, the entire microorganisms can also be used for the reaction according to the invention.
- the enzymes can be used in free or immobilized form, whereby all common immobilization methods can be used.
- the amount of enzyme can vary widely. It is selected depending on the size of the batch, the desired reaction time and the type of enzyme and can easily be determined in individual cases by simple preliminary tests.
- the substrate to be cleaved is in racemic form, i.e. used as a 1: 1 mixture of the S and R enantiomers.
- the optical yield can be increased by using already optically enriched substrate, resulting for example from enzymatic hydrolysis, crystallization or the like, for enzymatic cleavage.
- the cleavage is carried out in suspension, it being possible to set a substrate-buffer ratio of 0.1% by weight to 30% by weight, 1 to 10% by weight being preferred.
- the reaction is carried out at 10 to 65 ° C., preferably 20 to 50 ° C., the dependence of the activity of the particular enzyme on the temperature naturally having to be taken into account.
- the pH of the reaction solution is also in the range from pH 3 to 12, preferably 5 to 9, in particular between 6 and 8.5, depending on the activity of the enzyme.
- the enzyme / substrate ratio can range from 0.05% by weight to 100% by weight, but is preferably between 1 and 20% by weight. In the continuous column process, the local enzyme / substrate ratio caused by the concentration of the substrate solution can even exceed 100% by weight.
- the optical antipodes are in the form of carboxylic acid or vinyl ester and can be distilled according to their different physical or chemical behavior. Crystallization, chromatography or other common processes are separated, but preferably by extraction such that at an alkaline pH the ester is exhaustively extracted with a suitable organic solvent, such as chloroform, methylene chloride, tert-butyl methyl ether, methyl isobutyl ketone, etc., the acid initially remains as the alkali salt in the aqueous phase.
- the 2-arylpropionic acid can then be precipitated as an amorphous precipitate at a low pH (pH 1 to 4) and centrifuged or removed by extraction with the abovementioned solvents.
- the cleaved, optically enriched vinyl ester can be reacted in a repeated cleavage according to the process described above with the same or a different, opposite stereoselectivity enzyme.
- Optically active vinyl esters can be prepared from the corresponding 2-arylpropionic acids, surprisingly while maintaining full optical activity, by palladium-catalyzed transvinylation in vinyl acetate.
- Li 2 PdCl 4 on activated carbon is preferably used as the support material as catalyst.
- the transvinylation is preferably carried out at the boiling point of the reaction mixture.
- the 2-arylpropionic acid vinyl esters have a good anti-inflammatory effect.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- Microbiology (AREA)
- Analytical Chemistry (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Enzymes And Modification Thereof (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Furan Compounds (AREA)
- Pyrrole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3919029A DE3919029A1 (de) | 1989-06-10 | 1989-06-10 | Verfahren zur enzymatischen spaltung von 2-arylpropionsaeure-vinylester |
DE3919029 | 1989-06-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0402771A1 true EP0402771A1 (fr) | 1990-12-19 |
EP0402771B1 EP0402771B1 (fr) | 1994-11-30 |
Family
ID=6382512
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90110794A Expired - Lifetime EP0402771B1 (fr) | 1989-06-10 | 1990-06-07 | Procédé de dédoublement enzymatique d'esters vinyliques d'acides 2-aryl propioniques |
Country Status (5)
Country | Link |
---|---|
US (2) | US5155028A (fr) |
EP (1) | EP0402771B1 (fr) |
JP (1) | JPH0343095A (fr) |
CA (1) | CA2018562C (fr) |
DE (2) | DE3919029A1 (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0510712A2 (fr) * | 1991-04-26 | 1992-10-28 | Ministero Dell' Universita' E Della Ricerca Scientifica E Tecnologica | Procédé de séparation d'isomères optiques d'acides carboxyliques alpha-substitués |
WO1992020812A1 (fr) * | 1991-05-16 | 1992-11-26 | Valtion Teknillinen Tutkimuskeskus | Procede de production de composes chiraux utilises comme isomeres optiquement purs |
EP0517798A1 (fr) * | 1990-02-26 | 1992-12-16 | Rhone Poulenc Ind | Resolution stereospecifique d'acides 2-arylpropioniques par hydrolyse de leurs esters au moyen d'enzymes du foie. |
EP0997534A2 (fr) * | 1998-09-30 | 2000-05-03 | Basf Aktiengesellschaft | Procédé pour le dédoublement du mélange racémique d'esters arylalkyl d'acides carboxyliques |
EP1290209A1 (fr) * | 2000-06-01 | 2003-03-12 | SK Corporation | Procede de fabrication d'acide carboxylique heterocyclique a substitution alpha de forme r ou s, et de forme contre- enantiomere d'acide carboxylique heterocyclique a substitution alpha correspondante, a base d'enzyme |
EP1290208A1 (fr) * | 2000-06-01 | 2003-03-12 | SK Corporation | Procede de resolution optique d'un acide carboxylique heterocyclique alpha-substitue racemique a l'aide d'enzymes |
EP2003211A2 (fr) * | 2006-03-28 | 2008-12-17 | Sumitomo Chemical Company, Limited | Procede de production de (s)-7-hydroxy-6-methylheptane-2-one optiquement active et de precurseur de celle-ci |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7091023B2 (en) | 2000-08-07 | 2006-08-15 | Novozymes A/S | Stereoselective esterase from Aspergillus oryzae |
EP1398373A1 (fr) * | 2002-09-06 | 2004-03-17 | The Procter & Gamble Company | Lipase spécifique au carotène |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0153474A2 (fr) * | 1983-12-16 | 1985-09-04 | Roche Diagnostics GmbH | Procédé d'obtention de l'acide D-2-(6-méthoxy-2-napthyl)-propionique |
EP0195717A2 (fr) * | 1985-03-22 | 1986-09-24 | Montedison S.p.A. | Procédé de préparation biotechnologique d'acides alpha-arylalcanoiques optiquement actifs |
EP0299558A1 (fr) * | 1987-07-01 | 1989-01-18 | Gist-Brocades N.V. | Procédé de préparation d'ibuprofène |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3960893A (en) * | 1968-04-16 | 1976-06-01 | Imperial Chemical Industries Limited | Phenyl-thienyl-alkanoic acid derivatives and phenyl-furyl-alkanoic acid derivatives |
US4107178A (en) * | 1975-01-23 | 1978-08-15 | Sagami Chemical Research Center | Thioprene or furan derivatives and process for preparation thereof |
JPS5941966B2 (ja) * | 1975-10-21 | 1984-10-11 | 住友化学工業株式会社 | ガイチユウボウジヨソセイブツ オヨビ ソノセイゾウホウ |
US4266067A (en) * | 1977-03-18 | 1981-05-05 | Sagami Chemical Research Center | Process for preparing thiophene derivatives |
EP0023726B1 (fr) * | 1977-07-23 | 1982-05-19 | Beecham Group Plc | Acides méthyl penta-2,4-diénoiques-2,5 disubstitués,3-substitués, leurs dérivés, et procédé pour leur préparation |
EP0144832A3 (fr) * | 1983-12-06 | 1987-01-21 | F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft | Procédé de production de dérivés optiquement actifs de l'acide 3-hydroxypropionique substitué en alpha |
HU197942B (en) * | 1985-12-20 | 1989-06-28 | Wisconsin Alumni Res Found | Process for producing (s)-alpha-methyl-aryl-acetic acids |
GB8600245D0 (en) * | 1986-01-07 | 1986-02-12 | Shell Int Research | Preparation of 2-arylpropionic acids |
CA1283923C (fr) * | 1986-08-30 | 1991-05-07 | Hans-Juergen Neubauer | Furan- et thiophenecarboxylates de propargyle |
US4783473A (en) * | 1987-09-02 | 1988-11-08 | E. R. Squibb & Sons, Inc. | Geminally substituted cyclic ether carboxylic acids, derivatives thereof, compositions containing same and method of use |
DE3743824C2 (de) * | 1987-12-23 | 1997-03-06 | Hoechst Ag | Verfahren zur enzymatischen Racematspaltung von racemischen Alkoholen mit/in Vinylestern durch Umesterung |
FR2626289B1 (fr) * | 1988-01-27 | 1990-06-08 | Rhone Poulenc Sante | Procede de preparation d'acides aryl-2 alkanoiques optiquement actifs |
ATE138414T1 (de) * | 1988-04-21 | 1996-06-15 | Gist Brocades Nv | Verfahren zur herstellung von optisch aktiver 2- arylpropionsäure |
DE8807152U1 (de) * | 1988-06-01 | 1988-10-06 | Hohe Kg, 6981 Collenberg | Außenspiegel für ein Fahrzeug, insbesondere für einen Lastkraftwagen |
JPH06100066B2 (ja) * | 1989-08-01 | 1994-12-12 | 日立建機株式会社 | 多連シールド掘進機のカッタ同期運転装置 |
US4921798A (en) * | 1989-09-25 | 1990-05-01 | Eastman Kodak Company | Synthesis of (aryl or arylalkyl)-3-hydroxy propionic acids and aryl alkanediols having high optical purity |
-
1989
- 1989-06-10 DE DE3919029A patent/DE3919029A1/de not_active Withdrawn
-
1990
- 1990-06-07 EP EP90110794A patent/EP0402771B1/fr not_active Expired - Lifetime
- 1990-06-07 DE DE59007810T patent/DE59007810D1/de not_active Expired - Lifetime
- 1990-06-08 JP JP2148886A patent/JPH0343095A/ja active Pending
- 1990-06-08 US US07/535,149 patent/US5155028A/en not_active Expired - Lifetime
- 1990-06-08 CA CA002018562A patent/CA2018562C/fr not_active Expired - Lifetime
-
1992
- 1992-06-25 US US07/903,755 patent/US5426211A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0153474A2 (fr) * | 1983-12-16 | 1985-09-04 | Roche Diagnostics GmbH | Procédé d'obtention de l'acide D-2-(6-méthoxy-2-napthyl)-propionique |
EP0195717A2 (fr) * | 1985-03-22 | 1986-09-24 | Montedison S.p.A. | Procédé de préparation biotechnologique d'acides alpha-arylalcanoiques optiquement actifs |
EP0299558A1 (fr) * | 1987-07-01 | 1989-01-18 | Gist-Brocades N.V. | Procédé de préparation d'ibuprofène |
Non-Patent Citations (1)
Title |
---|
TETRAHEDRON LETTERS, Band 28, Nr. 9, 1987, Seiten 953-954, Pergamon Journals Ltd, GB; M. DEGUEIL-CASTAING et al.: "Enzymatic reactions in organic synthesis: 2- Ester interchange of vinyl esters" * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0517798A1 (fr) * | 1990-02-26 | 1992-12-16 | Rhone Poulenc Ind | Resolution stereospecifique d'acides 2-arylpropioniques par hydrolyse de leurs esters au moyen d'enzymes du foie. |
EP0517798A4 (en) * | 1990-02-26 | 1993-06-30 | Rhone-Poulenc Inc. | Stereospecific resolution by hydrolysis of esters of 2-arylpropionic acids by liver enzymes |
EP0510712A3 (en) * | 1991-04-26 | 1994-10-26 | Mini Ricerca Scient Tecnolog | Process for the separation of the optical isomers of alpha-substituted carboxylic acids |
EP0510712A2 (fr) * | 1991-04-26 | 1992-10-28 | Ministero Dell' Universita' E Della Ricerca Scientifica E Tecnologica | Procédé de séparation d'isomères optiques d'acides carboxyliques alpha-substitués |
WO1992020812A1 (fr) * | 1991-05-16 | 1992-11-26 | Valtion Teknillinen Tutkimuskeskus | Procede de production de composes chiraux utilises comme isomeres optiquement purs |
EP0997534A3 (fr) * | 1998-09-30 | 2003-09-03 | Basf Aktiengesellschaft | Procédé pour le dédoublement du mélange racémique d'esters arylalkyl d'acides carboxyliques |
EP0997534A2 (fr) * | 1998-09-30 | 2000-05-03 | Basf Aktiengesellschaft | Procédé pour le dédoublement du mélange racémique d'esters arylalkyl d'acides carboxyliques |
EP1290209A1 (fr) * | 2000-06-01 | 2003-03-12 | SK Corporation | Procede de fabrication d'acide carboxylique heterocyclique a substitution alpha de forme r ou s, et de forme contre- enantiomere d'acide carboxylique heterocyclique a substitution alpha correspondante, a base d'enzyme |
EP1290208A1 (fr) * | 2000-06-01 | 2003-03-12 | SK Corporation | Procede de resolution optique d'un acide carboxylique heterocyclique alpha-substitue racemique a l'aide d'enzymes |
EP1290208A4 (fr) * | 2000-06-01 | 2006-05-24 | Sk Corp | Procede de resolution optique d'un acide carboxylique heterocyclique alpha-substitue racemique a l'aide d'enzymes |
EP1290209A4 (fr) * | 2000-06-01 | 2006-05-24 | Sk Corp | Procede de fabrication d'acide carboxylique heterocyclique a substitution alpha de forme r ou s, et de forme contre- enantiomere d'acide carboxylique heterocyclique a substitution alpha correspondante, a base d'enzyme |
EP2003211A2 (fr) * | 2006-03-28 | 2008-12-17 | Sumitomo Chemical Company, Limited | Procede de production de (s)-7-hydroxy-6-methylheptane-2-one optiquement active et de precurseur de celle-ci |
EP2003211A4 (fr) * | 2006-03-28 | 2010-12-01 | Sumitomo Chemical Co | Procede de production de (s)-7-hydroxy-6-methylheptane-2-one optiquement active et de precurseur de celle-ci |
Also Published As
Publication number | Publication date |
---|---|
US5426211A (en) | 1995-06-20 |
CA2018562C (fr) | 2001-11-27 |
US5155028A (en) | 1992-10-13 |
DE3919029A1 (de) | 1990-12-13 |
EP0402771B1 (fr) | 1994-11-30 |
JPH0343095A (ja) | 1991-02-25 |
DE59007810D1 (de) | 1995-01-12 |
CA2018562A1 (fr) | 1990-12-10 |
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